Although some types of TiO 2 powders and gel-derived films can exhibit bioactivity, plasma-sprayed TiO 2 coatings are always bioinert, thereby hampering wider applications in bone implants. We have successfully produced a bioactive nanostructured TiO 2 surface with grain size smaller than 50 nm using nanoparticle plasma spraying followed by hydrogen plasma immersion ion implantation (PIII). The hydrogen PIII nano-TiO 2 coating can induce bone-like apatite formation on its surface after immersion in a simulated body fluid. In contrast, apatite cannot form on either the as-sprayed TiO 2 surfaces (both <50 nm grain size and >50 nm grain size) or hydrogen-implanted TiO 2 with grain size larger than 50 nm. Hence, both a hydrogenated surface that gives rise to negatively charged functional groups on the surface and small grain size (<50 nm) that enhances surface adsorption are crucial to the growth of apatite. Introduction of surface bioactivity to plasma-sprayed TiO 2 coatings, which are generally recognized to have excellent biocompatibility and corrosion resistance as well as high bonding to titanium alloys, makes them more superior than many current biomedical coatings.